EP0080223A2 - Enzymatic liquid detergent composition - Google Patents
Enzymatic liquid detergent composition Download PDFInfo
- Publication number
- EP0080223A2 EP0080223A2 EP82201395A EP82201395A EP0080223A2 EP 0080223 A2 EP0080223 A2 EP 0080223A2 EP 82201395 A EP82201395 A EP 82201395A EP 82201395 A EP82201395 A EP 82201395A EP 0080223 A2 EP0080223 A2 EP 0080223A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- amount
- enzyme
- liquid detergent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000003599 detergent Substances 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- 230000002255 enzymatic effect Effects 0.000 title claims abstract description 13
- -1 amino compound Chemical class 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 3
- 102000004190 Enzymes Human genes 0.000 claims description 18
- 108090000790 Enzymes Proteins 0.000 claims description 18
- 239000005864 Sulphur Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000011149 active material Substances 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 239000012736 aqueous medium Substances 0.000 claims 1
- 125000005619 boric acid group Chemical group 0.000 claims 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229940088598 enzyme Drugs 0.000 description 17
- 150000001639 boron compounds Chemical class 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 108091005804 Peptidases Proteins 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000004365 Protease Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000271 synthetic detergent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 102000035195 Peptidases Human genes 0.000 description 3
- 108010056079 Subtilisins Proteins 0.000 description 3
- 102000005158 Subtilisins Human genes 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000002538 fungal effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 241000194108 Bacillus licheniformis Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- KLRNMDPLGYEZCJ-AOWDYJTJSA-N (2s,3r)-butane-1,2,3,4-tetrol;(2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol Chemical compound OC[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO KLRNMDPLGYEZCJ-AOWDYJTJSA-N 0.000 description 1
- SSYDTHANSGMJTP-ZXZARUISSA-N (3s,4r)-oxolane-3,4-diol Chemical compound O[C@H]1COC[C@H]1O SSYDTHANSGMJTP-ZXZARUISSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- JVTIXNMXDLQEJE-UHFFFAOYSA-N 2-decanoyloxypropyl decanoate 2-octanoyloxypropyl octanoate Chemical compound C(CCCCCCC)(=O)OCC(C)OC(CCCCCCC)=O.C(=O)(CCCCCCCCC)OCC(C)OC(=O)CCCCCCCCC JVTIXNMXDLQEJE-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 102000004139 alpha-Amylases Human genes 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- 230000003625 amylolytic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001461 cytolytic effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
Abstract
Description
- The present invention relates to an aqueous liquid enzymatic detergent composition with improved enzyme- stability.
- Aqueous liquid enzymatic detergent compositions are well-known in the prior art. A major problem which is encountered with such compositions is that of ensuring a sufficient storage-stability of the enzymes in such compositions. The prior art has already described various ways in which this problem can be overcome, e.g. by inclusion of enzyme-stabilizing systems in such liquid detergent compositions.
- Thus, it has been proposed to include a mixture of a polyol and boric acid or an alkalimetalborate in an aqueous liquid enzymatic detergent composition. This system indeed increases the stability of the enzymes in liquid detergent compositions.
- It has also been proposed to include a mixture of a polyfunctional amino compound having at least one amine grouping and at least two hydroxyl groups and boric acid or an alkalimetalborate as enzyme-stabilizing system in aqueous liquid detergent compositions. This system also improves the enzyme storage stability in such detergent compositions.
- Recently, it has been proposed to use a mixture of a water-dispersible antioxidant and an organic, hydrophilic, water-soluble polyol having a molecular weight of less than about 500 as enzyme-stabilizing system in liquid detergent compositions. Preferably a buffering amount of a weak base, such as an alkanolamine, is also present in the enzymatic liquid detergent composition.
- It has now been found that a mixture of a polyol and/or a polyfunctional amino compound, with boric acid or an alkalimetalborate and with an antioxidant produces a synergistic enzyme-stabilizing effect, that is an effect which surmounts the sum-effect of each of the binary systems.
- It has been found that in the mixture of the invention the antioxidant must be present above a certain level, as well as the boric acid or the alkalimetalborate.
- The antioxidant should be present in the mixture in an amount of at least 5% by weight of the final enzymatic aqueous liquid detergent composition, and the boric acid or alkalimetalborate in an amount of at least 2% by weight of the final enzymatic aqueous liquid detergent composition.
- The polyol should be present in an amount at least equal to the amount of boric acid or alkalimetalborate, and the polyfunctional amino compound should be present in such an amount, that the weight ratio of this compound to the boric acid or alkalimetalborate is at least 0.5.
- The essential constituents of the mixture of the invention will now be further discussed in detail.
- The polyols that can be used in the present invention are polyols containing from 2 to 6 hydroxyl groups. They contain only C, H, and O atoms. Typical examples are ethyleneglycol, propyleneglycol, 1,2 propanediol, butyleneglycol, hexyleneglycol, glycerol, mannitol, sorbitol erythritol, glucose, fructose, lactose and erythritan (= 1,4-anhydride of erythritol). Preferably glycerol is used.
- In general, the amount of polyol used ranges from 2 to 25%, preferably from 5 to 15% by weight of the final composition.
- The polyfunctional amino compounds that can be used in the present invention contain at least one amine grouping and at least two hydroxylgroups. Suitable examples are diethanolamine, triethanolamine, di-isopropanolamine, tri-isopropanolamine, and tris(hydroxymethyl) aminomethane. It is to be understood that quaternary ammonium compounds are not included in the term polyfunctional amino compound. Preferably triethanolamine is used.
- In general, the amount of polyfunctional amino compound used ranges from 2 to 25, preferably from 4-15% by weight of the final composition.
- Mixtures of various polyols or various polyfunctional amino compounds may also be used, as well as mixtures of polyols and polyfunctional compounds.
- The boron compound that is used in the present invention is a boron compound which is capable of reacting with the polyol or polyfunctional amino compound. Suitable examples thereof are boric acid, boric oxide and alkali- metalborates such as sodium and potassium ortho-, meta-, and pyroborate, borax, and polyborates. Preferably the boron compound is borax.
- In general, the amount of boron compound used ranges from 2 to 15, preferably from 3.5-10% by weight of the final composition.
- The amount of polyol used should be at least equal to the amount of boron compound used in the final composition; generally the weight ratio of the amount of polyol to the amount of the boron compound ranges from 1 up to two, and preferably from 1 to 1.6.
- The amount of polyfunctional amino compound used should be at least half the amount of the boron compound used; generally the weight ratio of the amount of the polyfunctional amino compound to the amount of boron compound ranges from 1:2 to 10:1, preferably from 7:1 to 2:1.
- The boron compound is to be calculated on the basis of borax for all the above ranges.
- Mixtures of various boron compounds can also be used.
- The antioxidants that are used in the present invention are reducing alkalimetalsalts having an oxygenated sulphur anion SaOb in which a and b are numbers from 1 to 8. Typical examples of such reducing salts are alkalimetalsulphites, alkalimetalbisulphites, alkalimetabisulphites, alkalimetalthiosulphates, in which the alkalimetal is sodium or potassium. Of these, sodium sulphite is the preferred compound.
- The reducing alkalimetal salt is used in an amount ranging from 5-20, preferably from 6-15% by weight of the final compositions.
- The aqueous liquid compositions in which the stabilizing systems of the invention are incorporated are aqueous, liquid enzymatic detergent compositions further comprising as essential ingredients enzymes, and active detergents.
- The enzymes to be incorporated can be proteolytic, amylolytic and cellulolytic enzymes as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. Although the liquid compositions of the present invention may have a near-neutral pH value, the present invention is of particular benefit for enzymatic liquid detergents with a pH of 7.5 or above, especially those incorporating bacterial proteases of which the pH-optima lie in the range between 8.0 and 11.0, but it is to be understood that enzymes with a somewhat lower or higher pH-optimum can still be used in the compositions of the invention, benefiting from it.
- Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase R (ex Gist-Brocades N.V., Delft, Holland) and Alcalase R (ex Novo Industri A/S, Copenhagen, Denmark).
- As stated above, the present invention is of particular benefit for enzymatic liquid detergents incorporating enzymes with pH-activity and/or stability optima of above 8.0, such enzymes being commonly called high-alkaline enzymes.
- Particularly suitable is a protease obtained from a strain of Bacillus, having maximum activity throughout the pH-range of 8-12, developed and sold by Novo Industri A/S under the registered trade name of Esperase R. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
- High-alkaline amylases and cellulase can also be used, e.g. alpha-amylases obtained from a special strain of B. licheniformis, described in more detail in British Patent Specification No. 1,296,839 (Novo).
- The enzymes can be incorporated in any suitable form, e.g. as a granulate (marumes, prills etc.), or as a liquid concentrate. The granulate form has often advantages.
- The amount of enzymes present in the liquid composition may vary from 0.001 to 10% by weight, and preferably from 0.01 to 5% by weight.
- The liquid detergent compositions of the invention furthermore comprise as essential ingredient an active detergent material, which may be an alkali metal or alkanol amine soap or a C10-C24 fatty acid, including polymerized fatty acids, or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent material, or mixtures of any of these.
- Examples of anionic synthetic detergents are salts (including sodium, potassium, ammonium, and substituted ammonium salts such as mono-, die- and triethanolamine salts) of C9-C20 alkylbenzenesulphonates, C8-c22 primary or secondary alkanesulphonates, C8-c24 olefinsulphonates, sulphonated polycarboxylic acids, prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g. as described in British Patent Specification No. 1,082,179, C8-C22 alkylsulphates, C8-C24 alkylpolyglycolethersulphates (containing up to 10 moles of ethylene oxide); further examples are described in "Surface Active Agents and Detergents" (Vol. I and II) by Schwartz, Perry and Berch.
- Examples of nonionic synthetic detergents are the condensation products of ethylene oxide, propylene oxide and/or butyleneoxide with C8-C18 alkylphenols, C8-C18 primary or secondary aliphatic alcohols, C8-C18 fatty acid amides; further examples of nonionics include tertiary amine oxides with one C8-C18 alkyl chain and two C1-3 alkyl chains. The above reference also describes further examples of nonionics.
- The average number of moles of ethylene oxide and/or propylene oxide present in the above nonionics varies from 1-30; mixtures of various nonionics, including mixtures of nonionics with a lower and a higher degree of alkoxylation, may also be used.
- Examples of cationic detergents are the quaternary ammonium compounds such as alkyldimethylammonium halogenides, but such cationics are less preferred for inclusion in enzymatic detergent compositions.
- Examples of amphoteric or zwitterionic detergents are N-alkylamino acids, sulphobetaines, condensation products of fatty acids with protein hydrolysates, but owing to their relatively hight costs they are usually used in combination with an anionic or a nonionic detergent. Mixtures of the various types of active detergents may also be used, and preference is given to mixtures of an anionic and a nonionic detergent active. Soaps (in the form of their sodium, potassium, and substituted ammonium salts) of fatty acids may also be used, preferably in conjunction with an anionic and/or a nonionic synthetic detergent.
- The amount of the active detergent material varies from 1 to 60%, preferably from 2-40 and especially preferably from 5-25%; when mixtures of e.g. anionics and nonionics are used, the relative weight ratio varies from 10:1 to 1:10, preferably from 6:1 to 1:6. When a soap is also incorporated, the amount-thereof is from 1-40% by weight.
- The liquid compositions of the invention may further contain up to 60% of a suitable builder, such as sodium, potassium and ammonium or substituted ammonium pyro- and tripolyphosphates, -ethylenediamine tetraacetates, -nitrilotriacetates, -etherpolycarboxylates, -citrates, -carbonates, -orthophosphates, zeolites, carboxymethyl- oxysuccinate, etc. Particularly preferred are the polyphosphate builder salts, nitrilotriacetates,citrates, zeolites, and mixtures thereof. In general the builders are present in an amount of 1-60, preferably 5-50% by weight of the final composition.
- The amount of water present in the detergent compositions of the invention varies from 5 to 70% by weight.
- Other conventional materials may also be present in the liquid detergent compositions of the invention, for example soil-suspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, s±licates, optical brighteners, suds depressants such as silicones, germicides, anti-tarnishing agents, opacifiers, fabric softening agents, oxygen-liberating bleaches such as hydrogen peroxide, sodium perborate or percarbonate, disperiso- phthalic anhydride, with or without bleach precursors, buffers and the like. When the composition contains a builder, it may sometimes be advantageous to include a suspension stabilizer in the composition to provide a satisfactory phase-stability. Such stabilizers include natural or synthetic polymers, which however should not be capable of reacting with the boron compound. Suitable examples of such suspension stabilizers are polyacrylates, copolymers of maleic anhydride and ethylene or vinylmethylether, and polymers of acrylic acid, cross-linked with not more than 10% of a vinyl-group containing cross-linking agent, e.g. polymers of acrylic acid, cross-linked with about 1% of a polyallyl ether of sucrose having an average of about 5.8 alkylgroups for each sucrose molecule. Examples of the latter are commercially available products, available under the registered trade name of Carbopol 934, 940 and 941 of B.F. Goodrich Co Ltd.
- In general, if a suspension stabilizer is required, it will be included in an amount of 0.1-2, usually 0.25-1% by weight of the final composition.
- The invention will now be further illustrated by way of Example. In the examples, all the percentages are percentages by weight of the final composition.
- The pH of the final composition is near neutral, preferably higher than 7.5, and should preferably lie within the range of 8.0 to 10.0, and is, if necessary, buffered to a value within that range by addition of a suitable buffer system. The pH of the wash liquor, when using the composition, is about 1 pH unit higher than the above values at an in-use concentration of about 1%.
-
-
- As can be seen from series A-D, the mixtures of the invention produce an effect which clearly surmounts the sum effects of the individual binary mixtures.
- In series E, where there is less than the required 5% of the sulphite present, there is no such effect.
-
-
- Again this shows an unexpected increase in half-life time.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8134887 | 1981-11-19 | ||
GB8134887 | 1981-11-19 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0080223A2 true EP0080223A2 (en) | 1983-06-01 |
EP0080223A3 EP0080223A3 (en) | 1984-10-03 |
EP0080223B1 EP0080223B1 (en) | 1986-07-30 |
Family
ID=10525996
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82201395A Expired EP0080223B1 (en) | 1981-11-19 | 1982-11-08 | Enzymatic liquid detergent composition |
Country Status (11)
Country | Link |
---|---|
US (1) | US4462922A (en) |
EP (1) | EP0080223B1 (en) |
JP (1) | JPS5891800A (en) |
AR (1) | AR228215A1 (en) |
AU (1) | AU555411B2 (en) |
BR (1) | BR8206658A (en) |
CA (1) | CA1190494A (en) |
DE (1) | DE3272362D1 (en) |
NZ (1) | NZ202484A (en) |
PH (1) | PH18253A (en) |
ZA (1) | ZA828331B (en) |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0126505A1 (en) * | 1983-04-26 | 1984-11-28 | Unilever N.V. | Aqueous enzyme-containing compositions with improved stability |
DE3418295A1 (en) * | 1983-05-31 | 1984-12-06 | Colgate Palmolive Co | STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING AQUEOUS LIQUID DETERGENT |
DE3418294A1 (en) * | 1983-05-31 | 1984-12-06 | Colgate-Palmolive Co., New York, N.Y. | STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING LIQUID DETERGENT |
US4537707A (en) * | 1984-05-14 | 1985-08-27 | The Procter & Gamble Company | Liquid detergents containing boric acid and formate to stabilize enzymes |
US4537706A (en) * | 1984-05-14 | 1985-08-27 | The Procter & Gamble Company | Liquid detergents containing boric acid to stabilize enzymes |
GB2168375A (en) * | 1982-08-30 | 1986-06-18 | Colgate Palmolive Co | Stabilized enzyme-containing detergent compositions |
DE3623943A1 (en) * | 1985-07-26 | 1987-02-05 | Colgate Palmolive Co | STABILIZED, TEXTILE SOFTENING, ENZYME-BASED LIQUID DETERGENT |
DE3623942A1 (en) * | 1985-07-26 | 1987-04-16 | Colgate Palmolive Co | STABILIZED, ENZYMED LIQUID DETERGENT |
US4842758A (en) * | 1986-10-31 | 1989-06-27 | Colgate-Palmolive Company | Stabilized enzyme system for use in aqueous liquid built detergent compositions |
US4900475A (en) * | 1985-07-26 | 1990-02-13 | Colgate-Palmolive Co. | Stabilized built liquid detergent composition containing enzyme |
US4959179A (en) * | 1989-01-30 | 1990-09-25 | Lever Brothers Company | Stabilized enzymes liquid detergent composition containing lipase and protease |
EP0391253A1 (en) * | 1989-04-06 | 1990-10-10 | Henkel Kommanditgesellschaft auf Aktien | Purification method of enzyme solutions |
WO1990013632A1 (en) * | 1989-05-10 | 1990-11-15 | Henkel Kommanditgesellschaft Auf Aktien | Process for cleaning enzyme liquid concentrates |
EP0401661A1 (en) * | 1989-06-08 | 1990-12-12 | Henkel Kommanditgesellschaft auf Aktien | Liquid enzyme concentrate |
US5089163A (en) * | 1989-01-30 | 1992-02-18 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic liquid detergent composition |
EP0553607A1 (en) * | 1992-01-31 | 1993-08-04 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
EP0594924A1 (en) * | 1992-10-28 | 1994-05-04 | The Procter & Gamble Company | Process for the manufacture of a liquid detergent composition comprising a sulphiting agent and an enzyme system |
US5442100A (en) * | 1992-08-14 | 1995-08-15 | The Procter & Gamble Company | β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids |
US5445651A (en) * | 1992-01-31 | 1995-08-29 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
US5472628A (en) * | 1991-04-30 | 1995-12-05 | The Procter & Gamble Company | Liquid detergents with an aryl acid for inhibition of proteolytic enzyme |
US5476608A (en) * | 1991-12-04 | 1995-12-19 | The Procter & Gamble Company | Liquid laundry detergents with citric acid, cellulase, and boricdiol complex to inhibit proteolytic enzyme |
US5691295A (en) * | 1995-01-17 | 1997-11-25 | Cognis Gesellschaft Fuer Biotechnologie Mbh | Detergent compositions |
US5904736A (en) * | 1995-04-28 | 1999-05-18 | Henkel Kommanditgesellschaft Auf Aktien | Cellulase-containing washing agents |
US5972668A (en) * | 1994-06-28 | 1999-10-26 | Henkel Kommanditgesellschaft Auf Aktien | Production of multi-enzyme granules |
US6153576A (en) * | 1996-02-16 | 2000-11-28 | Henkel Kommanditgesellschaft Auf Aktien | Transition-metal complexes used as activators for peroxy compounds |
WO2003055974A2 (en) | 2001-12-22 | 2003-07-10 | Henkel Kommanditgesellschaft Auf Aktien | Novel alkaline protease from bacillus sp. (dsm 14392) and washing and cleaning products comprising said novel alkaline protease |
WO2004053042A1 (en) | 2002-12-06 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Multicomponent liquid detergent |
EP0780466B2 (en) † | 1995-12-22 | 2005-01-19 | Kao Corporation | Enzyme-containing granulated product, method of preparation, and compositions containing the granulated product |
WO2006045419A1 (en) * | 2004-10-21 | 2006-05-04 | Unilever Plc | Detergent composition |
US7431739B2 (en) | 2005-06-08 | 2008-10-07 | Henkel Kommanditgesellschaft Auf Aktien | Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol |
WO2009030728A2 (en) * | 2007-09-05 | 2009-03-12 | Novozymes A/S | Enzyme compositions with stabilizing constituent |
US8034123B2 (en) | 2005-06-08 | 2011-10-11 | Henkel Ag & Co., Kgaa | Boosting cleaning power of detergents by means of a polymer |
Families Citing this family (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4597889A (en) * | 1984-08-30 | 1986-07-01 | Fmc Corporation | Homogeneous laundry detergent slurries containing polymeric acrylic stabilizers |
US4560492A (en) * | 1984-11-02 | 1985-12-24 | The Procter & Gamble Company | Laundry detergent composition with enhanced stain removal |
US5296161A (en) * | 1986-06-09 | 1994-03-22 | The Clorox Company | Enzymatic perhydrolysis system and method of use for bleaching |
US5364554A (en) * | 1986-06-09 | 1994-11-15 | The Clorox Company | Proteolytic perhydrolysis system and method of use for bleaching |
US4711739A (en) * | 1986-12-18 | 1987-12-08 | S. C. Johnson & Son, Inc. | Enzyme prespotter composition stabilized with water insoluble polyester or polyether polyol |
US4800037A (en) * | 1987-06-05 | 1989-01-24 | Lever Brothers Company | Process for making a heavy duty liquid detergent composition |
JPS64895U (en) * | 1987-06-17 | 1989-01-05 | ||
AU3667189A (en) * | 1988-06-23 | 1990-01-04 | Unilever Plc | Enzyme-containing liquid detergents |
EP0431747B1 (en) * | 1989-11-30 | 1996-11-20 | The Clorox Company | Stable liquid aqueous oxidant detergent |
US5073292A (en) * | 1990-06-07 | 1991-12-17 | Lever Brothers Company, Division Of Conopco, Inc. | Heavy duty liquid detergent compositions containing enzymes stabilized by quaternary nitrogen substituted proteins |
JPH0775620B2 (en) * | 1991-04-08 | 1995-08-16 | トーメー産業株式会社 | Liquid formulation for hydrous contact lens and method for washing hydrous contact lens |
US5356800A (en) * | 1992-11-30 | 1994-10-18 | Buckman Laboratories International, Inc. | Stabilized liquid enzymatic compositions |
US6710259B2 (en) * | 1993-05-17 | 2004-03-23 | Electrochemicals, Inc. | Printed wiring boards and methods for making them |
US6303181B1 (en) | 1993-05-17 | 2001-10-16 | Electrochemicals Inc. | Direct metallization process employing a cationic conditioner and a binder |
US6171468B1 (en) | 1993-05-17 | 2001-01-09 | Electrochemicals Inc. | Direct metallization process |
WO1995002673A1 (en) * | 1993-07-15 | 1995-01-26 | The Procter & Gamble Company | LOW pH GRANULAR DETERGENT COMPOSITION HAVING IMPROVED BIODEGRADABILITY |
CA2177997C (en) * | 1993-12-03 | 2008-09-23 | James C. Lee | Enzyme stabilization by block-copolymers |
US5494817A (en) * | 1993-12-06 | 1996-02-27 | Allergan, Inc. | Sugar-based protease composition for use with constant-PH borate buffers |
US5474701A (en) * | 1994-01-21 | 1995-12-12 | Buckman Laboratories International, Inc. | Enzymes for recreational water |
CA2161975C (en) * | 1994-03-21 | 2000-02-01 | Jeanne A. O'brien | Stable enzyme-containing aqueous laundry prespotting composition |
EP0795009A1 (en) * | 1994-12-28 | 1997-09-17 | Genencor International Inc. | Enzyme stabilization |
US5604190A (en) * | 1995-06-07 | 1997-02-18 | Alcon Laboratories, Inc. | Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems |
US5723421A (en) * | 1995-06-07 | 1998-03-03 | Alcon Laboratories, Inc. | Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems |
US6184189B1 (en) | 1995-06-07 | 2001-02-06 | Alcon Laboratories, Inc. | Liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems |
US5576278A (en) * | 1995-06-07 | 1996-11-19 | Alcon Laboratories, Inc. | Stable liquid enzyme compositions and methods of use |
US5672213A (en) * | 1995-08-18 | 1997-09-30 | Alcon Laboratories, Inc. | Liquid enzyme compositions containing aromatic acid derivatives |
US5605661A (en) * | 1995-08-18 | 1997-02-25 | Alcon Laboratories, Inc. | Methods of using liquid enzyme compositions containing mixed polyols |
US6214596B1 (en) | 1996-12-18 | 2001-04-10 | Alcon Laboratories, Inc. | Liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems |
US6060441A (en) * | 1997-04-10 | 2000-05-09 | Henkel Corporation | Cleaning compositions having enhanced enzyme activity |
DE19725508A1 (en) | 1997-06-17 | 1998-12-24 | Clariant Gmbh | Detergents and cleaning agents |
HUP0600532A2 (en) * | 1998-12-16 | 2006-10-28 | Unilever Nv | Transparent/translucent liquid enzyme compositions in clear bottles comprising antioxidants |
AR017744A1 (en) * | 1999-02-08 | 2001-09-12 | Procter & Gamble | POLYMERIC GLYCOLS AND DIOLES FOR IMPROVED DETERGENT COMPOSITIONS FOR THE WASHING OF VAJILLA |
JP2003512509A (en) * | 1999-10-15 | 2003-04-02 | ザ、プロクター、エンド、ギャンブル、カンパニー | Enzyme liquid cleaning composition |
US6835703B1 (en) | 1999-12-30 | 2004-12-28 | Melaleuca, Inc. | Liquid automatic dishwashing detergent |
EP1153892A1 (en) * | 2000-05-08 | 2001-11-14 | Realco 2001 S.A./N.V. | Cleaning product containing enzymes |
ES2208611T3 (en) | 2000-06-15 | 2004-06-16 | Unilever N.V. | COMPOSITION OF CONCENTRATED LIQUID DETERGENT. |
US20050164902A1 (en) * | 2003-10-24 | 2005-07-28 | Ecolab Inc. | Stable compositions of spores, bacteria, and/or fungi |
US6624132B1 (en) * | 2000-06-29 | 2003-09-23 | Ecolab Inc. | Stable liquid enzyme compositions with enhanced activity |
US7795199B2 (en) | 2000-06-29 | 2010-09-14 | Ecolab Inc. | Stable antimicrobial compositions including spore, bacteria, fungi, and/or enzyme |
US7569532B2 (en) | 2000-06-29 | 2009-08-04 | Ecolab Inc. | Stable liquid enzyme compositions |
AU2002233186A1 (en) | 2000-11-28 | 2002-06-11 | Henkel Kommanditgesellschaft Auf Aktien | Cyclodextrin glucanotransferase (cgtase), obtained from bacillus agaradherens (dsm 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase |
US20020183226A1 (en) * | 2001-02-28 | 2002-12-05 | Chandrika Kasturi | Liquid detergent composition exhibiting enhanced alpha-amylase enzyme stability |
CN1575308B (en) | 2001-10-22 | 2010-04-28 | 汉高两合股份公司 | Cotton active, dirt removing urethane-based polymers |
DE10153792A1 (en) | 2001-10-31 | 2003-05-22 | Henkel Kgaa | New alkaline protease variants and washing and cleaning agents containing these new alkaline protease variants |
DE10162728A1 (en) | 2001-12-20 | 2003-07-10 | Henkel Kgaa | New alkaline protease from Bacillus gibsonii (DSM 14393) and washing and cleaning agents containing this new alkaline protease |
DE10162727A1 (en) | 2001-12-20 | 2003-07-10 | Henkel Kgaa | New alkaline protease from Bacillus gibsonii (DSM 14391) and washing and cleaning agents containing this new alkaline protease |
US7448556B2 (en) | 2002-08-16 | 2008-11-11 | Henkel Kgaa | Dispenser bottle for at least two active fluids |
GB0417332D0 (en) * | 2004-08-04 | 2004-09-08 | Reckitt Benckiser Nv | Improvements in aqueous compositions |
CN101072872A (en) * | 2004-12-09 | 2007-11-14 | 陶氏环球技术公司 | Enzyme stabilization |
US20080025960A1 (en) * | 2006-07-06 | 2008-01-31 | Manoj Kumar | Detergents with stabilized enzyme systems |
US7915213B2 (en) * | 2007-04-27 | 2011-03-29 | Church & Dwight Co., Inc. | High ash liquid laundry detergents comprising a urea and/or glycerine hygroscopic agent |
US7964548B2 (en) | 2009-01-20 | 2011-06-21 | Ecolab Usa Inc. | Stable aqueous antimicrobial enzyme compositions |
US7723281B1 (en) | 2009-01-20 | 2010-05-25 | Ecolab Inc. | Stable aqueous antimicrobial enzyme compositions comprising a tertiary amine antimicrobial |
DE102009047764A1 (en) * | 2009-12-10 | 2011-06-16 | Evonik Goldschmidt Gmbh | Release agent and use for the production of composite moldings |
US8933131B2 (en) | 2010-01-12 | 2015-01-13 | The Procter & Gamble Company | Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same |
CN103380204B (en) | 2011-02-17 | 2016-02-03 | 宝洁公司 | Comprise the composition of the mixture of C10-C13 alkyl benzene sulfonate |
WO2012112828A1 (en) | 2011-02-17 | 2012-08-23 | The Procter & Gamble Company | Bio-based linear alkylphenyl sulfonates |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2748212A1 (en) * | 1976-11-01 | 1978-05-11 | Unilever Nv | ENZYMATIC LIQUID DETERGENT |
DE2748211A1 (en) * | 1976-11-01 | 1978-05-11 | Unilever Nv | ENZYMATIC LIQUID DETERGENT |
US4261868A (en) * | 1979-08-08 | 1981-04-14 | Lever Brothers Company | Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound |
GB2079305A (en) * | 1980-07-02 | 1982-01-20 | Unilever Plc | Liquid enzyme detergent |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2095300A (en) * | 1928-01-07 | 1937-10-12 | Wallerstein Co Inc | Process of increasing activity of proteolytic enzymes |
US3741901A (en) * | 1970-08-07 | 1973-06-26 | Pabst Brewing Co | Washing compositions and process |
DK152074A (en) * | 1973-03-22 | |||
US4243543A (en) * | 1979-05-11 | 1981-01-06 | Economics Laboratory, Inc. | Stabilized liquid enzyme-containing detergent compositions |
US4268406A (en) * | 1980-02-19 | 1981-05-19 | The Procter & Gamble Company | Liquid detergent composition |
-
1982
- 1982-11-02 US US06/438,665 patent/US4462922A/en not_active Expired - Lifetime
- 1982-11-08 EP EP82201395A patent/EP0080223B1/en not_active Expired
- 1982-11-08 DE DE8282201395T patent/DE3272362D1/en not_active Expired
- 1982-11-12 NZ NZ202484A patent/NZ202484A/en unknown
- 1982-11-12 ZA ZA828331A patent/ZA828331B/en unknown
- 1982-11-15 AU AU90466/82A patent/AU555411B2/en not_active Ceased
- 1982-11-15 PH PH28140A patent/PH18253A/en unknown
- 1982-11-16 AR AR291307A patent/AR228215A1/en active
- 1982-11-18 JP JP57202830A patent/JPS5891800A/en active Granted
- 1982-11-18 BR BR8206658A patent/BR8206658A/en not_active IP Right Cessation
- 1982-11-18 CA CA000415822A patent/CA1190494A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2748212A1 (en) * | 1976-11-01 | 1978-05-11 | Unilever Nv | ENZYMATIC LIQUID DETERGENT |
DE2748211A1 (en) * | 1976-11-01 | 1978-05-11 | Unilever Nv | ENZYMATIC LIQUID DETERGENT |
US4261868A (en) * | 1979-08-08 | 1981-04-14 | Lever Brothers Company | Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound |
GB2079305A (en) * | 1980-07-02 | 1982-01-20 | Unilever Plc | Liquid enzyme detergent |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2168375A (en) * | 1982-08-30 | 1986-06-18 | Colgate Palmolive Co | Stabilized enzyme-containing detergent compositions |
GB2168376A (en) * | 1982-08-30 | 1986-06-18 | Colgate Palmolive Co | Stabilized enzyme-containing detergent compositions |
EP0126505A1 (en) * | 1983-04-26 | 1984-11-28 | Unilever N.V. | Aqueous enzyme-containing compositions with improved stability |
DE3418295A1 (en) * | 1983-05-31 | 1984-12-06 | Colgate Palmolive Co | STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING AQUEOUS LIQUID DETERGENT |
DE3418294A1 (en) * | 1983-05-31 | 1984-12-06 | Colgate-Palmolive Co., New York, N.Y. | STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING LIQUID DETERGENT |
US4537707A (en) * | 1984-05-14 | 1985-08-27 | The Procter & Gamble Company | Liquid detergents containing boric acid and formate to stabilize enzymes |
US4537706A (en) * | 1984-05-14 | 1985-08-27 | The Procter & Gamble Company | Liquid detergents containing boric acid to stabilize enzymes |
US4900475A (en) * | 1985-07-26 | 1990-02-13 | Colgate-Palmolive Co. | Stabilized built liquid detergent composition containing enzyme |
DE3623942A1 (en) * | 1985-07-26 | 1987-04-16 | Colgate Palmolive Co | STABILIZED, ENZYMED LIQUID DETERGENT |
DE3623943A1 (en) * | 1985-07-26 | 1987-02-05 | Colgate Palmolive Co | STABILIZED, TEXTILE SOFTENING, ENZYME-BASED LIQUID DETERGENT |
US4842758A (en) * | 1986-10-31 | 1989-06-27 | Colgate-Palmolive Company | Stabilized enzyme system for use in aqueous liquid built detergent compositions |
US4959179A (en) * | 1989-01-30 | 1990-09-25 | Lever Brothers Company | Stabilized enzymes liquid detergent composition containing lipase and protease |
US5089163A (en) * | 1989-01-30 | 1992-02-18 | Lever Brothers Company, Division Of Conopco, Inc. | Enzymatic liquid detergent composition |
EP0391253A1 (en) * | 1989-04-06 | 1990-10-10 | Henkel Kommanditgesellschaft auf Aktien | Purification method of enzyme solutions |
WO1990012089A1 (en) * | 1989-04-06 | 1990-10-18 | Henkel Kommanditgesellschaft Auf Aktien | Process for cleaning enzyme solutions |
WO1990013632A1 (en) * | 1989-05-10 | 1990-11-15 | Henkel Kommanditgesellschaft Auf Aktien | Process for cleaning enzyme liquid concentrates |
EP0401661A1 (en) * | 1989-06-08 | 1990-12-12 | Henkel Kommanditgesellschaft auf Aktien | Liquid enzyme concentrate |
WO1990015129A1 (en) * | 1989-06-08 | 1990-12-13 | Henkel Kommanditgesellschaft Auf Aktien | Fluid enzyme concentrate |
US5472628A (en) * | 1991-04-30 | 1995-12-05 | The Procter & Gamble Company | Liquid detergents with an aryl acid for inhibition of proteolytic enzyme |
US5476608A (en) * | 1991-12-04 | 1995-12-19 | The Procter & Gamble Company | Liquid laundry detergents with citric acid, cellulase, and boricdiol complex to inhibit proteolytic enzyme |
EP0553607A1 (en) * | 1992-01-31 | 1993-08-04 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
US5445651A (en) * | 1992-01-31 | 1995-08-29 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer in washing |
TR26494A (en) * | 1992-01-31 | 1995-03-15 | Procter & Gamble | DETERGENT COMPOSITIONS THAT PREVENT DYEING THROUGH WASH |
US5442100A (en) * | 1992-08-14 | 1995-08-15 | The Procter & Gamble Company | β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids |
EP0594924A1 (en) * | 1992-10-28 | 1994-05-04 | The Procter & Gamble Company | Process for the manufacture of a liquid detergent composition comprising a sulphiting agent and an enzyme system |
US5972668A (en) * | 1994-06-28 | 1999-10-26 | Henkel Kommanditgesellschaft Auf Aktien | Production of multi-enzyme granules |
US5691295A (en) * | 1995-01-17 | 1997-11-25 | Cognis Gesellschaft Fuer Biotechnologie Mbh | Detergent compositions |
US5855625A (en) * | 1995-01-17 | 1999-01-05 | Henkel Kommanditgesellschaft Auf Aktien | Detergent compositions |
US5904736A (en) * | 1995-04-28 | 1999-05-18 | Henkel Kommanditgesellschaft Auf Aktien | Cellulase-containing washing agents |
EP0780466B2 (en) † | 1995-12-22 | 2005-01-19 | Kao Corporation | Enzyme-containing granulated product, method of preparation, and compositions containing the granulated product |
US6153576A (en) * | 1996-02-16 | 2000-11-28 | Henkel Kommanditgesellschaft Auf Aktien | Transition-metal complexes used as activators for peroxy compounds |
WO2003055974A2 (en) | 2001-12-22 | 2003-07-10 | Henkel Kommanditgesellschaft Auf Aktien | Novel alkaline protease from bacillus sp. (dsm 14392) and washing and cleaning products comprising said novel alkaline protease |
WO2004053042A1 (en) | 2002-12-06 | 2004-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Multicomponent liquid detergent |
WO2006045419A1 (en) * | 2004-10-21 | 2006-05-04 | Unilever Plc | Detergent composition |
US7431739B2 (en) | 2005-06-08 | 2008-10-07 | Henkel Kommanditgesellschaft Auf Aktien | Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol |
US8034123B2 (en) | 2005-06-08 | 2011-10-11 | Henkel Ag & Co., Kgaa | Boosting cleaning power of detergents by means of a polymer |
WO2009030728A2 (en) * | 2007-09-05 | 2009-03-12 | Novozymes A/S | Enzyme compositions with stabilizing constituent |
WO2009030728A3 (en) * | 2007-09-05 | 2009-05-07 | Novozymes As | Enzyme compositions with stabilizing constituent |
Also Published As
Publication number | Publication date |
---|---|
AU555411B2 (en) | 1986-09-25 |
US4462922A (en) | 1984-07-31 |
EP0080223B1 (en) | 1986-07-30 |
JPS5891800A (en) | 1983-05-31 |
AU9046682A (en) | 1983-05-26 |
PH18253A (en) | 1985-05-13 |
EP0080223A3 (en) | 1984-10-03 |
NZ202484A (en) | 1985-05-31 |
DE3272362D1 (en) | 1986-09-04 |
ZA828331B (en) | 1984-06-27 |
AR228215A1 (en) | 1983-01-31 |
CA1190494A (en) | 1985-07-16 |
JPS6116796B2 (en) | 1986-05-02 |
BR8206658A (en) | 1983-10-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0080223B1 (en) | Enzymatic liquid detergent composition | |
EP0126505B1 (en) | Aqueous enzyme-containing compositions with improved stability | |
EP0080748B1 (en) | Enzymatic liquid cleaning composition | |
CA1163218A (en) | Liquid enzymatic detergent composition | |
US4261868A (en) | Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound | |
CA1092036A (en) | Enzymatic liquid detergent compositions | |
EP0139329B1 (en) | Dishwashing compositions | |
US5089163A (en) | Enzymatic liquid detergent composition | |
US4537706A (en) | Liquid detergents containing boric acid to stabilize enzymes | |
US4465619A (en) | Built liquid detergent compositions | |
US5039446A (en) | Liquid detergent with stabilized enzyme | |
CA2008389C (en) | Enzymatic liquid detergent composition | |
US4537707A (en) | Liquid detergents containing boric acid and formate to stabilize enzymes | |
GB1286899A (en) | Enzyme-containing detergent compositions | |
EP0348183A2 (en) | Enzyme-containing liquid detergents | |
AU618036B2 (en) | Machine dishwashing compositions | |
US5501820A (en) | Aqueous enzymatic detergent compositions | |
CA1092037A (en) | Enzymatic liquid detergent composition | |
EP0842254B1 (en) | Dingy fabric clean-up with amylase enzyme in detergent compositions | |
AU610286B2 (en) | Enzymatic liquid detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): DE FR GB IT NL |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: UNILEVER PLC Owner name: UNILEVER NV |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Designated state(s): DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19840804 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 3272362 Country of ref document: DE Date of ref document: 19860904 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19941007 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19941024 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19941026 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19941130 Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19951108 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19960601 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19951108 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19960731 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19960601 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19960801 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |